Inorganic Chemistry Applications of UV-Visible Absorption and

Circular Dichroism Spectroscopy

George E Tranter, Chiralabs Limited, Oxfordshire, UK
& 2010 Elsevier Ltd. All rights reserved.

Abbreviations
CD
CT
MCD
UV

circular dichroism
charge transfer
magnetic circular dichroism
ultraviolet

UV-visible absorption spectroscopy is an invaluable

method of investigating the structure and the behavior of
inorganic compounds, especially the coordination complexes of transition metals, lanthanides, and actinides.
Not only are the spectra characteristic of the metal ion,
its ligands, and coordination geometry, but they are also
informative of its electronic state. Changes in complexation can be followed readily, and the technique is often
the one of choice to monitor kinetics of inorganic reactions, complexations, and rearrangements with time,
temperature, or other environmental factors.
In the case of chiral compounds, the use of circular
dichroism (CD) spectroscopy is invaluable and adds not
just an insight into the handedness of the structures but
also a further elucidation of their electronic configuration
due to the differing selection rules of the spectral transitions. As an extension, by the application of a magnetic
field, magnetic circular dichroism (MCD) can yield
structural information on both chiral and achiral complexes, especially those with nonsinglet spin states.

Complexes
The classical type of complex has a central metal ion
surrounded by coordinating ligands, with little electronic
delocalization between them, such that the ligandmetal
bonding is essentially ionic. As such, the central metal ion
can be assigned a formal charge, as can the ligands where
appropriate. However, this is an idealized case and there
are many examples where there is significant electron
delocalization between the metal ion and the ligands,
such that the bonding has a degree of covalent character;
such complexes are better described as nonclassical or
covalent complexes. Moreover, multicentered complexes,
with multiple metal ions, are well represented. There is
no a priori condition on the phase in which metal complexes can exist and arrays of ions in a crystalline phase
can be regarded as simply extended complexes. Thus, a
gamut of inorganic systems falls under the broad

description of metal complexes in terms of their spectroscopic behavior.

Most investigations are performed on solutions of
complexes. However, studies on the solid crystalline
state, with the crystal aligned at specific orientations to
ensure excitation to selected states, can aid the interpretation of spectra enormously. As a corollary, the study
of oriented crystalline solids by absorption and CD can
provide a characterization of the packing arrangement
and interactions occurring within the crystal.

Spectral Features
Many of the spectral features of metal complexes in the
near-UV (ultraviolet) and visible wavelength regions are
primarily derived from the formally electric dipolar
forbidden dd (for transition metals) and ff (for lanthanides and actinides) transitions of the metal ions. Such
metal-centered transitions exhibit inherently weak
absorptions, the bands corresponding to quadrupole and
higher-order electric multipole transitions or magnetic
dipole transitions (cf. crystal field theory), enhanced by
coupled/induced electric dipolar contributions from the
ligands (cf. ligand polarization theory). It is not unusual
for the molar absorptivities (extinction coefficients) of
dd- and ff-derived bands to be of the order of e E 0.1
100 M1 cm1. Although generally weak compared to
formally electric dipole allowed transitions, the spectral
features are distinctive and can be determined with even
basic UV-visible absorption spectrometers. However,
absorptions primarily derived from the ligands may also
be evident and may dominate the weaker features.
In contrast, chiral complexes can yield relatively
substantial CD spectra especially where the features
derive from metal-centered magnetic dipole-allowed
transitions; the ligands undergo charge transfer (CT)
transitions or are in an inherently chiral arrangement and
have their own electric dipole-allowed transitions that
may take part in exciton coupling (CD exciton coupling
is explained further under its own section in this
encyclopedia).

Spectral Interpretation and Computation

Although, ideally, theories to rationalize the spectra of
metal mixing complexes should fully contain the

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Inorganic Chemistry Applications of UV-Visible Absorption and Circular Dichroism Spectroscopy

confounding aspects of covalency, delocalization, and state

(e.g., multielectron multiconfiguration molecular orbital
theories), often simpler theories are sufficient for spectral
interpretation. In practice, the use of crystal field and
ligand polarization theories remains adequate to at least
semiquantitatively explain the observed spectral features,
provided the metal-ion states are adequately described, i.e.,
including the effects of spinorbit coupling and Casimir
operators (for lanthanides and actinides).
Although crystal field theory concentrates on the
static electrostatic effect of the ligands on the metal ion,
ligand polarization theory describes the dynamic effect of
coupling between the ligand polarizability and the metalion transitions. The combination of crystal field and
ligand polarization theories to yield the local systems
theory enables a good first approximation for rationalization of spectra, in terms of both wavelength and intensity of the absorptions. Moreover, the local systems
theory can often be very effective in explaining the CD of
chiral metal complexes, both when the CD is derived
primarily from the metal-centered transitions and when
electronic coupling within the ligands is dominant. Indeed, it provides a sound basis for the hypersensitive
transitions that display a significant dependence between
ligand type and absorption or CD intensity.

possesses D3 symmetry but pseudo-octahedral coordination by the amine nitrogens, which has direct consequences for the spectral features observed both in the
solution and the solid state.
It is readily apparent that the different states, described in terms of their pseudo-octahedral (Oh) and D3
symmetry, impart differing spectral characteristics. In
particular, the CT transition, in which charge is transferred from the ligand NCo s bond to a metal-centered
s* antibonding orbital, displays a huge absorption compared to the other transitions, primarily due to its electric
transition dipole mechanism. Importantly, this band and
magnetic dipole-allowed transition I1 also display significantly larger CD bands than the other transitions.

[Cobalt (ethylenediamine)3]3 Example

The details of the absorption and CD strengths can also
prove diagnostic in describing the electronic states of a
complex. Table 1 details a classic example of a cobalt trisethylenediamine complex (derived from the work of
Mason 1982). This complex has a chiral, propeller-like
structure, the hand of which is determined by the conformation/configuration of the ethylenediamine ligands
around the cobalt ion. The L(ddd) ( )589 stereoisomer,
one of eight possibilities (four of each hand), is depicted in
Figure 1. It can be seen that this particular configuration

Figure 1 L(ddd) stereoisomer of ( )589 [cobalt

(ethylenediamine)3]3, with its central cobalt(III) ion and
surrounding three ethylenediamine molecules arranged in a
propeller fashion, with D3 symmetry but pseudo-octahedral
coordination by the amine nitrogens. Copyright (2009), with
permission from Chiralabs Ltd.

Table 1 UV-visible absorption and circular dichroism solution spectra of ( )589 [cobalt (ethylenediamine)3]3, with terms and
symbols relating to the Oh (D3) symmetry of the complex
Transition

Electronic states

Wavelength
(nm)

A
B
I1

740
590

I2
II1
II2
CT

A1g3T1g spin forbidden

A1g3T2g spin forbidden
1
A1g1T1g (1A2) spin allowed, magnetic
dipole allowed
1
A1g1T1g (1E) spin allowed, magnetic
dipole allowed
1
A1g1T2g (1A1) spin allowed, magnetic
dipole forbidden
1
A1g1T2g (1E) spin allowed, magnetic
dipole allowed
s(N)s*(Co) charge transfer
1

470

Absorption e
(M1 cm1)
0.3
1

Circular dichroism
De (M1 cm1)

Kuhns
dissymmetry
factor DeX e

 0.002
0.025
1.9

 0.007
0.025
0.02

84
 0.17
0.003

340

74

210

15 000

0.25

 31

 0.002

Inorganic Chemistry Applications of UV-Visible Absorption and Circular Dichroism Spectroscopy

Notably, from solid-state studies in which only certain

excited states are accessed by judicious choice of crystal
orientation, it can be seen that the I1 and I2 CD bands are
substantially larger than appears in solution, their apparent magnitude diminished due to cancellation of their
oppositely signed CD intensities.
The literature on the absorption and CD spectroscopy
of inorganic complexes has a long history and is extensive; the reader is directed to the review articles indicated
in the Further Reading section for both a historical and
current perspective. The reader is also directed to the
other articles in this encyclopedia covering UVvisible
absorption, CD, and MCD spectroscopies in general.
See also: Applications of Circular Dichroism, Chiroptical
Spectroscopy, General Theory, Circular Dichroism
Spectrometers, ORD and Polarimetry Instruments.

Further Reading
Burgess C and Knowles A (eds.) (1981) Techniques in Visible and
Ultraviolet Spectrometry, vol. 1: Standards in Absorption
Spectrometry. London: Chapman & Hall.
Burgess C and Knowles A (eds.) (1984) Techniques in Visible and
Ultraviolet Spectrometry, vol. 3: Practical Absorption Spectrometry.
London: Chapman & Hall.

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Clark BJ, Frost T, and Russell MA (eds.) (1993) Techniques in Visible

and Ultraviolet Spectrometry, vol. 4: UV Spectroscopy. London:
Chapman & Hall.
Hughes JL and Krausz E (2007) Electronic spectroscopy. In: Scott RA
and Lukehart CM (eds.) Encyclopedia of Inorganic Chemistry
Methods and Applications, Applications of Physical Methods to
Inorganic and Bioinorganic Chemistry, pp. 7998. Chichester, UK:
Wiley InterScience.
Kuroda R and Saito Y (1994) Circular dichroism of inorganic
complexes: Interpretation and applications. In: Nakanishi K,
Berova N, and Woody RW (eds.) Circular Dichroism Principles and
Applications, pp. 217--258. New York: Wiley VCH.
Mack J and Stillman MJ (2008) Magnetic circular dichroism (MCD)
spectroscopy. In: Scott RA and Lukehart CM (eds.) Encyclopedia of
Inorganic Chemistry Methods and Applications, Applications of
Physical Methods to Inorganic and Bioinorganic Chemistry, pp.
189204. Chichester, UK: Wiley InterScience.
Mason SF (1982) Molecular Optical Activity and the Chiral
Discriminations. Cambridge, UK: Cambridge University Press.
Mattis DA and Bashford CL (eds.) (1987) Spectrophotometry and
Spectrofluorometry: A Practical Approach. Oxford, UK: IRL.
Presta P.A. Stillman M.J. Circular dichroism (CD) spectroscopy
In: Scott RA and Lukehart CM (eds.) Encyclopedia of Inorganic
Chemistry Methods and Applications, Applications of Physical
Methods to Inorganic and Bioinorganic Chemistry, pp. 1-16.
Chichester, UK: Wiley InterScience.
Tranter GE (1984) Theoretical Studies of Parity Breaking in Molecular
Systems. PhD Thesis, Kings College London, pp. 1398.
Saito Y (1979) Inorganic Molecular Dissymmetry. New York:
SpringerVerlag.